CN85102991B - High temp. thermistor with high reproducibility - Google Patents
High temp. thermistor with high reproducibility Download PDFInfo
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- CN85102991B CN85102991B CN85102991A CN85102991A CN85102991B CN 85102991 B CN85102991 B CN 85102991B CN 85102991 A CN85102991 A CN 85102991A CN 85102991 A CN85102991 A CN 85102991A CN 85102991 B CN85102991 B CN 85102991B
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Abstract
The present invention relates to a high-temperature thermal resistor used at 100 DEG C to 500 DEG C, which belongs to the field of a semiconductor sensor. The thermal resistor uses magnesium-aluminium-manganese-nickel-cobalt serial oxide materials for selecting material constituents with the high reproducibility of resistance value by thermal-treatment characteristic tests. A high-temperature resistant glass tube is used for encapsulation, and the high-temperature thermal resistor is manufactured by high temperature, alternating temperature and ageing. The high-temperature thermal resistor has the characteristics of favorable reproducibility of resistance value, high-temperature long-term stability, small volume, reliable structure, rapid thermal response time, etc. and is especially suitable for aerospace and other military industrial departments, and simultaneously, the high-temperature thermal resistor can be widely used for domestic electric apparatuses, thermal meters, electronic tools and other fields of production and scientific research.
Description
The present invention relates to a kind of high-temperature thermistor and manufacture method thereof.
As everyone knows, use cobalt sesquioxide (Co
2O
3)-manganese dioxide (MnO
2)-nickel oxide (NiO)-cupric oxide (CuO) material can be made the high precision thermosensitive resistor device that uses below 300 ℃.And zirconium dioxide (ZrO
2)-yttria (Y
2O
3) series material can be used to make high-temperature thermistor, influences greatlyyer but this class material is pressed by oxygen, high temperature long-term ageing stability fails well to solve.The electric industry pearl of PANASONIC formula commercial firm uses magnesium aluminate (MgAl
2O
4)+chromic acid lanthanum (LaCrO
2) series material, make the high-temperature thermistor (patent No. J5334836) that different warm areas are used between 100 ℃-1000 ℃, but because it is a long-term ageing stability with material serves as according to selecting material, therefore can not guarantee after the various thermal processs of experience, still to have good resistance reproducibility, and that the resistance reproducibility plays a part practical application is very important.The encapsulation of high-temperature thermistor has metal tube encapsulation (200 ℃～800 ℃) (patent No. J50119267) and glass cladding (below 500 ℃) (Japanese metering device 1982.11P14) usually.The metal tube encapsulation, technology is comparatively complicated, and glass cladding shape structure has higher requirement to the coefficient of linear expansion of glass material, the coefficient of linear expansion of glass and sensitive body is bad as mating, the thermal stress that then causes thus will seriously have influence on the resistance reproducibility of high-temperature thermistor, even make element complete failure.
The present invention is directed to the problems referred to above, select the sensitive body material with new method, obtain the good material prescription of resistance reproducibility thus, cooperate the improvement on the manufacture method simultaneously, producing can be 100 ℃ of-600 ℃ of use, has good resistance reproducibility and stability, the simple high-temperature thermistor of structural manufacturing process.
The sensitive body material that the present invention selects for use is magnesium oxide (MgO)-alundum (Al (Al
2O
3)-manganese dioxide (MnO
2)-nickel oxide (NiO)-cobalt sesquioxide (Co
2O
3) the series ceramic material.High-temperature thermistor of the present invention is the resistance reproducibility of high spot reviews material after experience elevated temperature heat process when selecting material, and adopted the foundation that is used as weighing material resistance reproducibility with the characteristic after the quick cooling processing of high temperature.Its method is as follows, at first the thermo-sensitive material sample is heat-treated 300 ℃, 400 ℃, 500 ℃, 600 ℃ temperature, treatment conditions are insulation 10-30 minute, cooling fast in the air, each back resistance value during a certain fixed temperature between measuring 100 ℃-300 ℃ of handling, calculate the resistance varying-ratio of this fixed temperature point after heat treatments at different then, after being chosen in the different temperature points processing of using in the warm area, the little material of the maximum rate of change of the resistance of this fixed temperature point is made the high-temperature thermistor of this warm area, its performance test of Xingqi of going forward side by side.The high-temperature heat-sensitive material of Xuan Zeing had both solved the resistance reproducibility after various elevated temperature heat processes in this way, also had good high-temperature long-term ageing stability simultaneously.Table 1 has been listed magnesium oxide (MgO)-alundum (Al (Al
2O
3)-manganese dioxide (MnO
2)-nickel oxide (NiO)-cobalt sesquioxide (Co
2O
3) the B value and the Standard resistance range of atomic ratio, sintering condition and sample of some material prescriptions of series material, sample is the pearl body of φ 1.2mm.Table 2, table 3, table 4, table 5 have been listed the sample of above-mentioned material respectively, and in the resistance of a certain fixed temperature point, heat treatment time is 15 minutes after heat treatments at different, and air cools off fast.By table as can be seen, in the above-mentioned series material, the resistance reproducibility of the material prescription of 5 yuan of series after fast cooling heat treatment obviously is better than 3 yuan of systems and 4 yuan of based materials.When the atomic ratio of each composition during respectively at magnesium (2-4), aluminium (0.3-1), manganese (1-3), nickel (0.5-1.5), cobalt (1.5-4), its material constant B is (4000-5000) K, resistance is (0.5-20) K Ω in the time of 300 ℃, after the fast cooling heat treatment of 300 ℃, 400 ℃, 500 ℃, 600 ℃ several temperature points, the maximum rate of change of 200 ℃ of resistances is between 1% to 4%.Wherein, when each atoms of elements ratio is: magnesium: aluminium: manganese: nickel: cobalt=3.8: 1: 2: in the time of 0.9: 2.3, its material constant B is 4200K, and the maximum rate of change of 200 ℃ resistance is 1% after above-mentioned heat treatment.Employing is R after above-mentioned heat treatment
200Maximum rate of change less than 2%, the B value is at (4000-5000) K, resistance R
300(1-20) material prescription of K Ω is made 100 ℃ of-500 ℃ of high-temperature thermistors, can obtain good resistance reproducibility and high-temperature stability.
High-temperature thermistor of the present invention is a bead thermistor device of doing the tubulose encapsulation with resistant to elevated temperatures glass, and its appearance structure as shown in drawings.Responsive to temperature body (1) is the globule of φ 1.2mm among the figure, makes electrode with the platinum filament (2) of φ 0.1mm, and encapsulates with pyroceram (3), goes between with the platinum filament (4) of φ 0.2mm.
Main manufacture craft of the present invention is as follows: weighing-grinding-globule moulding-sintering-spot welding-encapsulation-high temperature ageing-alternating temperature wears out-the screening packing.Raw material ground 20 hours in agate mortar after pressing the formula rate mixing, added adhesive then; On the platinum filament that two parallel diameters are 0.1mm, put into globule, between 1600 ℃-1650 ℃ constant temperature 3-6 hour.Packing forms has a significant impact the performance of thermistor, and we have adopted the encapsulation of glass tubular type, not directly contact between glass and the sensitive body, and in order to improve the adhesive effect of platinum lead-in wire and glass, it is 65 * 10 that seal glass adopts coefficient of linear expansion
-7/ ℃ platinum-80 flint glass F or coefficient of linear expansion be (60 * 10
-7-100 * 10
-7)/℃ other pyroceram.Earlier an end of glass tube is sealed during encapsulation, be cut into certain length, the pearl body of the lead-in wire of burn-oning is put into pipe, under 900 ℃-1000 ℃ high temperature, tail end is obturaged.Element needs through high temperature ageing and alternating temperature aging.The high temperature ageing condition is 600 ℃ of temperature, 10 days time.Alternating temperature is aging to be in order further to improve the resistance reproducibility of element, and the present invention has adopted at 520 ℃ of aging 6 days-450 ℃ of aging 6 days-400 ℃ of aging 6 days-500 ℃ of aging 4 days-450 ℃ of alternating temperatures of aging 4 days of temperature alternately aging.With Mg: Al: Mn: Ni: Co=3.8: 1: 2: 0.9: 2.3 material sample was an example, compare with the sample that only carries out high temperature ageing (600 ℃ 20 days) through the sample of above-mentioned ageing process, high temperature ageing stability (600 ℃ 100 hours, 〈 ﹠﹠〉the alternating temperature ageing stability refer to 600 ℃, 500 ℃, 400 ℃, 300 ℃ aging respectively 24 hours, measure after each ageing process 300 ℃ resistance, the maximum value rate of change of obtaining thus.
Because what high-temperature thermistor of the present invention had changed common employing comes the way of chosen material according to high temperature long-term ageing stability, but set about from heat treatment characteristic, resistance reproducibility after the high spot reviews thermal process, the material of Xuan Zeing had both had good resistance reproducibility like this, had higher high-temperature stability again.On technology, taked alternating temperature alternately aging, from and further improved the performance of element.The structure of high-temperature thermistor has adopted glass tubular type encapsulation, and technology is simple, reliable in structure, volume is little, in light weight, thermal response time short.Therefore it can be widely used in space flight and military project department, also can be used as the observing and controlling temperature element of this warm area simultaneously in household appliances, electronic tool, Thermal Meter and other field.
Embodiment.Material prescription: atomic ratio is a magnesium: aluminium: manganese: nickel: cobalt=3.8: 1: 2: 0.9: 2.3, after the material mixing with this proportioning, ground 20 hours in agate mortar, add 2% adhesive, being shaped to the platinum filament spacing is 0.3mm, the pearl body is the globule of φ 1.2mm, 1620 ℃ of constant temperature 4 hours, the platinum filament of spot welding φ 0.2mm was lead-in wire, made tubular type with platinum-80 glass and encapsulated, glass size is φ (1.8 ± 0.2) mm, and long L is (0.6-0.8) mm.With packaged element earlier through 600 ℃ aging 10 days, it is aging to carry out alternating temperature by following condition again, 520 ℃ aging 6 days-450 ℃ aging 6 days-400 ℃ aging 6 days-500 ℃ aging 4 days-450 ℃ aging 4 days.The element of Zhi Zuoing like this, after 300 ℃, 400 ℃, 500 ℃, 600 ℃ rapid cooling thermals were handled 15 minutes respectively, the maximum rate of change of 200 ℃ resistance was 1%, R
500Be (8～20) K Ω, material constant B is 4200K, and high temperature ageing stability and some high temperature electrology characteristics of this high-temperature thermistor are as follows:
600 ℃ were worn out 24 hours, measured the resistance of 300 ℃ of aging front and back, and its resistance varying-ratio is less than 1%.
400 ℃ added 3 volts of voltages aging 1000 hours, measured the resistance of 300 ℃ of aging front and back, and its maximum rate of change is less than 3%.
300 ℃, 400 ℃, 500 ℃, 600 ℃ were worn out 24 hours respectively, measured the resistance of 300 ℃ of aging front and back, and its resistance varying-ratio is all less than 2%.
After the 600 ℃-room temperature circulation 1000 times, measure the resistance of 300 ℃ of circulation front and back, its resistance varying-ratio is less than 2%.
Claims (5)
1, a kind of is sensitive body with slug type pearl shape pottery, the glass tube encapsulation, with the platinum wire is electrode outlet line, the high-temperature thermistor of in 100 ℃～500 ℃ warm areas, working, it is characterized in that the material component of thermo-detective material is: magnesium oxide, alundum (Al, manganese dioxide, nickel oxide and cobalt sesquioxide.Each atoms of elements is than being magnesium (2-4), aluminium (0.3-1), manganese (1-3), nickel (0.5-1.5), cobalt (1.5-4), and its material constant is 4000K-5000K.
2, according to the thermistor of claim 1, the atomic ratio that it is characterized in that the thermo-detective material material component is Mg: Al: Mn: Ni: Co=3.8: 1: 2: 0.9: 2.3.Material constant is 4200K.
3,, it is characterized in that used packaged glass is that platinum-80 flint glass F or coefficient of linear expansion are (60-100) * 10 according to the thermistor of claim 1
-7/ ℃ other pyrocerams.
4, a kind of is sensitive body with slug type pearl pottery, glass packaging, with the platinum wire is electrode outlet line, the manufacture method of the high-temperature thermistor of working in 100 ℃～500 ℃ warm areas is characterized in that sample was handled respectively 10-30 minute with method for rapid cooling under 300 ℃, 400 ℃, 500 ℃, 600 ℃ temperature.In 100 ℃～300 ℃ warm areas, measure, the change in resistance of thermo-detective material, the maximum rate of change of the resistance after the selection heat treatment is 2%, its material constant is made high-temperature thermistor for the material of (4000～5000) K.
According to the manufacture method of the thermistor of claim 4, it is characterized in that 5, thermistor is aging through the high temperature alternating temperature, the aging technique process is: 600 ℃, 10 days-520 ℃, 6 days-450 ℃, 6 days-400 ℃, 6 days-500 ℃, 4 days-450 ℃, 4 days.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85102991A CN85102991B (en) | 1985-04-01 | 1985-04-01 | High temp. thermistor with high reproducibility |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85102991A CN85102991B (en) | 1985-04-01 | 1985-04-01 | High temp. thermistor with high reproducibility |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85102991A CN85102991A (en) | 1987-01-17 |
| CN85102991B true CN85102991B (en) | 1988-04-06 |
Family
ID=4792901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85102991A Expired CN85102991B (en) | 1985-04-01 | 1985-04-01 | High temp. thermistor with high reproducibility |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85102991B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046051C (en) * | 1996-12-14 | 1999-10-27 | 中国科学院新疆物理研究所 | Oxidate semiconductor thermosensitive resistance and mfg. method thereof |
| CN1046049C (en) * | 1996-12-14 | 1999-10-27 | 中国科学院新疆物理研究所 | Oxidate semi-conductor thermosensitive resistance and mfg. method thereof |
| CN1046048C (en) * | 1996-12-14 | 1999-10-27 | 中国科学院新疆物理研究所 | Oxidate semi-condcutor thermo-sensitive resistance and mfg. method thereof |
| CN1046050C (en) * | 1996-12-14 | 1999-10-27 | 中国科学院新疆物理研究所 | Oxidate semi-conductor thermosensitive resistance and mfg. method thereof |
| CN1046052C (en) * | 1996-12-14 | 1999-10-27 | 中国科学院新疆物理研究所 | Oxidate semi-conductor thermosensitive resistance and mfg. method thereof |
| CN102682944A (en) * | 2012-06-04 | 2012-09-19 | 句容市博远电子有限公司 | Negative temperature coefficient (NTC) thermosensitive resistor material |
| CN104515601B (en) * | 2013-10-08 | 2017-06-27 | 黄川� | Platinum electrode negative tempperature coefficient thermistor hemisphere microballon infrared focal plane array panel |
| CN107328833A (en) * | 2017-07-11 | 2017-11-07 | 北京科技大学 | The high temperature resistant wire beam electrode and preparation method characterized for combined material chip |
-
1985
- 1985-04-01 CN CN85102991A patent/CN85102991B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN85102991A (en) | 1987-01-17 |
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